Solution-phase synthesis of 2-cyano and 2-amido aziridinyl peptides

Fioravanti, Stefania; Massari, Davide; Morreale, Alberto; Pellacani, Lucio; Tardella, Paolo A.

doi:10.1016/j.tet.2008.01.098

Cited by 17 publications

(6 citation statements)

References 35 publications

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“…Further transformations include careful selection of conditions for aziridine deprotection and partial hydrolysis of the cyano group (Scheme 71) [119].…”

Section: Other Nosyloxycarbamatesmentioning

confidence: 99%

Ethyl Nosyloxycarbamate: A Chameleonic Aminating Agent

Pellacani¹,

Fioravanti²,

Tardella

2011

COC

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The purpose of this review is to illustrate the use of ethyl nosyloxycarbamate (NsONHCO(2)Et). This is a versatile aminating agent known for over 47 years and used to generate, in the presence of organic or inorganic bases under homogeneous conditions, a carbonyl nitrene, a reactive intermediate able to form new C-N or X-N bonds by electrophilic amination reaction of a remarkable variety of nucleophilic substrates. Interest in this reagent has been renewed most recently, during the past dozen years. Operating still in alkaline medium, but under generally heterogeneous conditions, has made possible new synthetic applications for the conjugate base of the same nosyloxycarbamate. These, developed mainly by our research group, allow to carry out direct syntheses of various nitrogenated compounds under mild conditions. The applications span from simple molecules to highly functionalized compounds and many new exciting regio- and stereoselective routes can be envisioned. In particular, it was possible to obtain aziridines containing a cornucopia of assorted functions and therefore able to provide access to more complex molecules under simple operational conditions by using an aminating agent cheap and easy to obtain

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“…Further transformations include careful selection of conditions for aziridine deprotection and partial hydrolysis of the cyano group (Scheme 71) [119].…”

Section: Other Nosyloxycarbamatesmentioning

confidence: 99%

Ethyl Nosyloxycarbamate: A Chameleonic Aminating Agent

Pellacani¹,

Fioravanti²,

Tardella

2011

COC

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“…Interested in extending our studies, our synthetic strategy was also applied to a-alkoxycarbonyl a 0 -carbamoyl aziridines (Fioravanti et al 2008(Fioravanti et al , 2009), more complex compounds that can be regarded as interesting building blocks for the synthesis of modified retro-peptides containing electrophilic sites. Their synthesis was obtained by direct amination reaction of the corresponding (E)-acrylonitriles (Fioravanti et al 2004) using ethyl nosyloxycarbamate (NsONHCO 2 Et, Ns = 4-NO 2 C 6 H 4 SO 2 ) as the aminating agent under heterogeneous conditions (Pellacani et al 2011).…”

Section: Resultsmentioning

confidence: 99%

“…HRMS and ES Q-TOF analyses were performed using a Micromass Q-TOF spectrometer equipped with an ESI source and a syringe pump. Compounds 6a-h were obtained as reported before (Fioravanti et al 2008).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of gem-diamino acid derivatives by a Hofmann rearrangement

et al. 2012

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Starting from commercially available N-protected L-α-amino acids, N,N'-protected gem-diaminic units were obtained by a two-step methodology. A Hofmann reaction performed using a primary alcohol as the solvent to trap the isocyanate intermediate represents the key step of the new synthetic procedure. Then, the methodology was applied to α-carbamoyl α'-carboxyl aziridines, also functionalized with L-α-amino esters and stable gem-diaminic units characterized by an aziridine ring and by a retro-peptide modification were obtained. The use of the latter units in the retro-peptide chemistry allows to obtain modified peptides containing an aziridine ring able to behave as an electrophilic site and as a biomimetic structural analog of proline.

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“…In recent years, the most efficient methods for the synthesis of aziridines are via carbene and nitrene, but generally these approaches are mainly suitable for unfunctionalized alkenes (19–24). Although Darzens‐type reaction and other related processes can provide alternative methods for the preparation of functionalized aziridines (25–36), there is almost no report about the preparation of cyano aziridines until now (37,38). Thus, searching for the simple and efficient synthetic approaches for the preparation of cyano aziridines with readily available starting materials becomes a great challenge.…”

Section: Optimizing the Reaction Catalystamentioning

confidence: 99%

One‐Pot Highly Stereoselective Synthesis of Cyano Aziridines via the CuCl‐Catalyzed Aminochlorination of α,β‐Unsaturated Nitriles and Intramolecular S_N2 Substitution

et al. 2010

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An efficient one-pot system has been developed for the synthesis of cyano aziridine by using a,bunsaturated nitriles as the alkene substrates and N,N-dichloro-p-toluenesulfonamide (4-TsNCl 2 ) as the nitrogen source. A good scope of alkene substrates was achieved for this reaction. The one-pot reaction, via aminohalogenation and intramolecular S N 2 substitution, was very convenient to carry out at room temperature without the protection of inert gases. Modest to good yields and excellent have been obtained. This method provides an easy route to the cyano aziridine. The structure of the resulting products has been unambiguously confirmed by X-ray structural analysis.

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Solution-phase synthesis of 2-cyano and 2-amido aziridinyl peptides

Cited by 17 publications

References 35 publications

Ethyl Nosyloxycarbamate: A Chameleonic Aminating Agent

Ethyl Nosyloxycarbamate: A Chameleonic Aminating Agent

Synthesis of gem-diamino acid derivatives by a Hofmann rearrangement

One‐Pot Highly Stereoselective Synthesis of Cyano Aziridines via the CuCl‐Catalyzed Aminochlorination of α,β‐Unsaturated Nitriles and Intramolecular S_N2 Substitution

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Solution-phase synthesis of 2-cyano and 2-amido aziridinyl peptides

Cited by 17 publications

References 35 publications

Ethyl Nosyloxycarbamate: A Chameleonic Aminating Agent

Ethyl Nosyloxycarbamate: A Chameleonic Aminating Agent

Synthesis of gem-diamino acid derivatives by a Hofmann rearrangement

One‐Pot Highly Stereoselective Synthesis of Cyano Aziridines via the CuCl‐Catalyzed Aminochlorination of α,β‐Unsaturated Nitriles and Intramolecular SN2 Substitution

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One‐Pot Highly Stereoselective Synthesis of Cyano Aziridines via the CuCl‐Catalyzed Aminochlorination of α,β‐Unsaturated Nitriles and Intramolecular S_N2 Substitution